Photocatalytic reduction of Cr(VI) in aqueous solutions by UV irradiation with the presence of titanium dioxide

The reduction of Cr(VI) in aqueous solution by UV/TiO2 reduction process was studied under various solution pH values, TiO2 dosages, light intensities, dissolved oxygen levels and other operating conditions. The reduction rates of Cr(VI) by photocatalytic-induced elections were significantly higher for acidic solutions than those for alkaline solutions. Increasing the light intensity would drastically increase the reduction rate of Cr(VI), but was ultimately influenced by the amount of TiO2 present in solutions. The presence of dissolved oxygen had minimum effect on the reduction of Cr(VI) by UV/TiO2 process in acidic solutions. The presence of ethanol might act as scavenger for holes and promoted the photocatalytic reduction of Cr(VI) by electrons. The Cr(VI) adsorbed on the surface of TiO2 particles was observed to be photoreduced to Cr(III) almost completely.     

Microscale geochemical gradients in Hanford 300 Area sediment biofilms and influence of uranium

The presence and importance of microenvironments in the subsurface at contaminated sites were suggested by previous geochemical studies. However, no direct quantitative characterization of the geochemical microenvironments had been reported. We quantitatively characterized microscale geochemical gradients (dissolved oxygen (DO), H₂, pH, and redox potential) in Hanford 300A subsurface sediment biofilms. Our results revealed significant differences in geochemical parameters across the sediment biofilm/water interface in the presence and absence of U(VI) under oxic and anoxic conditions. While the pH was relatively constant within the sediment biofilm, the redox potential and the DO and H₂ concentrations were heterogeneous at the microscale (<500-1000 μm). We found microenvironments with high DO levels (DO hotspots) when the sediment biofilm was exposed to U(VI). On the other hand, we found hotspots (high concentrations) of H₂ under anoxic conditions both in the presence and in the absence of U(VI). The presence of anoxic microenvironments inside the sediment biofilms suggests that U(VI) reduction proceeds under bulk oxic conditions. To test this, we operated our biofilm reactor under air-saturated conditions in the presence of U(VI) and characterized U speciation in the sediment biofilm. U L_III-edge X-ray absorption spectroscopy (XANES and EXAFS) showed that 80-85% of the U was in the U(IV) valence state.     

Mobilization of Cr(VI) from chromite ore processing residue through acid treatment

Batch leaching studies on chromite ore processing residue (COPR) were performed using acids to investigate leaching of hexavalent chromium, Cr(VI), with respect to particle size, reaction time, and type of acid (HNO(3) and H(2)SO(4)). Aqueous Cr(VI) is maximized at approximately 0.04 mol Cr(VI) per kg of dry COPR at pH 7.6-8.1. Cr(VI) mobilized more slowly for larger particles, and the pH increased with time and increased more rapidly for smaller particles, suggesting that rate limitations occur in the solid phase. With H(2)SO(4), the pH stabilized at a higher value (8.8 for H(2)SO(4) vs. 8.0 for HNO(3)) and more rapidly (16 h vs. 30 h), and the differences in pH for different particle sizes were smaller. The acid neutralization capacity (ANC) of COPR is very large (8 mol HNO(3) per kg of dry COPR for a stable eluate pH of 7.5). Changes to the elemental and mineralogical composition and distribution in COPR particles after mixing with acid indicate that Cr(VI)-bearing solids dissolved. However, concentrations of Cr(VI) >2800 mg kg(-1) (>50% of the pre-treatment concentration) were still found after mixing with acid, regardless of the particle size, reaction time, or type of acid used. The residual Cr(VI) appears to be partially associated with poorly-ordered Fe and Al oxyhydroxides that precipitated in the interstitial areas of COPR particles. Remediation strategies that use HNO(3) or H(2)SO(4) to neutralize COPR or to maximize Cr(VI) in solution are likely to require extensive amounts of acid, may not mobilize all of the Cr(VI), and may require extended contact time, even under well-mixed conditions.     

Abiotic reduction of dinitroaniline herbicides

The importance of abiotic reductive transformations as a sink for four dinitroaniline herbicides (trifluralin, pendimethalin, nitralin, and isopropalin) has been evaluated. Using reductants representative of abiotic reductants found in natural systems, the results of this study indicate that nitro groups present on the dinitroaniline herbicides can be reduced by surface-bound Fe(II) species in goethite suspensions or by hydroquinone moieties such as (mercapto)juglone in a hydrogen sulfide solution. Aqueous iron species are also effective at pH values above 7.0. The reaction in aqueous Fe(II) and in Fe(II)/goethite systems is strongly pH dependent, with rates increasing with increasing pH. Montmorillonite clay, however, is not effective in mediating the reduction of dinitroaniline herbicides in the presence of Fe(II). Because the selected dinitroaniline herbicides have a mixture of electron withdrawing and electron donating groups, linear free energy relationships were developed for the H(2)S/(mercapto)juglone and Fe(II)/goethite systems. Anilines resulting from reduction of the nitro group as well as cyclization products (benzimidazoles) were observed in the degradation of trifluralin. Only one aniline product was observed for pendimethalin.     

Mechanism of hexavalent chromium adsorption by persimmon tannin gel

Mechanism of chromium adsorption by the persimmon tannin (PT) gel was examined. The PT gel can adsorb Cr highly effectively from aqueous solutions containing Cr(VI), while it adsorbed far smaller amounts of Cr from the solution containing Cr(III). The maximum Cr adsorption from the Cr(VI) solution occurred at pH 3. The Cr adsorption from the Cr(VI) solution by the PT gel was rapid, was faster than VO2+ and Fe3+ adsorptions, and was obeyed the Langmuir adsorption isotherm (Qe= 5.27 mmol g(-1) and K= 16.2 mM). The gel adsorbed Cr from the Cr(VI) solution (pH 1 and 3) showed no ESR signal of Cr(III), while the ESR signal of Cr(III) was observed in the residual solution at pH 1. Hexavalent chromium was, therefore, adsorbed on the PT gel through the esterification of chromate with catechol group. In other words, Cr(VI) should combine with catechol as a hard acid, CrO2(2+) cation. Through the treatment of a Cr(VI) solution with the PT gel, chromium should be recovered as a Cr(IV)-tannin complex at pH 3 or a Cr(III) solution at pH 1 or lower pH region.     

Effects of dissolved oxygen on formation of corrosion products and concomitant oxygen and nitrate reduction in zero-valent iron systems with or without aqueous Fe2+

Batch tests were conducted in zero-valent iron (ZVI or Fe0) systems to investigate oxygen consumption and the effect of dissolved oxygen (DO) on formation of iron corrosion products, nitrate reduction, the reactivity of Fe0, the role Fe2+ (aq) played, and the fate of Fe2+. The study indicates that without augmenting Fe2+ (aq), neither nitrate nor DO could be removed efficiently by Fe0. In the presence of Fe2+ (aq), nitrate and DO could be reduced concomitantly with limited interference with each other. Unlike nitrate reduction, DO removal by Fe0 did not consume Fe2+ (aq). A two-layer structure, with an inner layer of magnetite and an outer layer of lepidocrocite, may be formed in the presence of DO. When DO depleted, the outer lepidocrocite layer was transformed to magnetite. The inner layer of magnetite, even in a substantial thickness, might not impede the Fe0 reactivity as much as the thin interfacial layer between the oxide coating and liquid. Surface-bound Fe2+ may greatly enhance the electron transfer from the Fe0 core to the solid-liquid interface, and thus improve the performance of the Fe0 process.     

Influences of humic acid, bicarbonate and calcium on Cr(VI) reductive removal by zero-valent iron

The influences of various geochemical constituents, such as humic acid, HCO₃⁻, and Ca²⁺, on Cr(VI) removal by zero-valent iron (Fe⁰) were investigated in a batch setting. The collective impacts of humic acid, HCO₃⁻, and Ca²⁺ on the Cr(VI) reduction process by Fe⁰ appeared to significantly differ from their individual impacts. Humic acid introduced a marginal influence on Fe⁰ reactivity toward Cr(VI) reduction, whereas HCO₃⁻ greatly enhanced Cr(VI) removal by maintaining the solution pH near neutral. The Cr(VI) reduction rate constants (k_obs) were increased by 37.8% and 78.3%, respectively, with 2 mM and 6 mM HCO₃⁻ in solutions where humic acid and Ca²⁺ were absent. Singly present Ca²⁺ did not show a significant impact to Cr(VI) reduction. However, probably due to the formation of passivating CaCO₃, further addition of Ca²⁺ to HCO₃⁻ containing solutions resulted in a decrease of k_obs compared to solutions containing HCO₃⁻ alone. Ca²⁺ enhanced humic acid adsorption led to a minor decrease of Cr(VI) reduction rates. In Ca²⁺-free solutions, humic acid increased the amount of total dissolved iron to 25 mg/l due to the formation of soluble Fe-humate complexes and stably dispersed fine Fe (oxy)hydroxide colloids, which appeared to suppress iron precipitation. In contrast, the coexistence of humic acid and Ca²⁺ significantly promoted the aggregation of Fe (oxy)hydroxides, with which humic acid co-aggregated and co-precipitated. These aggregates would progressively be deposited on Fe⁰ surfaces and impose long-term impacts on the permeability of PRBs.     

Removal of trivalent and hexavalent chromium with aminated polyacrylonitrile fibers: performance and mechanisms

Aminated polyacrylonitrile fibers (APANFs) were prepared and used as an adsorbent in a series of batch adsorption experiments for the removal of Cr(III) and Cr(VI) species from aqueous solutions of different pH values. The results show that significant amounts of Cr(III) or Cr(VI) species can be adsorbed by the APANFs, although the adsorption performances was greatly dependent upon the solution pH values. In general, the amounts of adsorption for Cr(III) species increased whereas that for Cr(VI) decreased with the increase of the solution pH values, which suggests that different adsorption mechanisms dominated the removal of Cr(III) or Cr(VI) species on the APANFs. X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy revealed that the adsorption of Cr(III) species on the APANFs was largely attributed to the formation of surface complexes between the nitrogen atoms on the APANFs and the Cr(III) species adsorbed, but the adsorption of Cr(VI) species on the APANFs was more likely effected through the formation of hydrogen bonds at high solution pH values or through both electrostatic attraction and surface complexation at low solution pH values. It was found that the Cr(VI)-adsorbed APANFs can be effectively regenerated in a basic solution and be reused almost without any loss of the adsorption capacity, while the Cr(III)-adsorbed APANFs needed to be regenerated in an acidic solution and the regeneration appeared to be less effective.     

Kinetics of chromium transformations in the environment

Kinetics of chromium transformations under typical environmental conditions were systematically investigated using batch, microcosm and column experiments. Oxidation and reduction rates were evaluated in single phase water systems and in two phase water-solid systems. Natural and reference waters, sediments and soils representing a broad range of characteristics were used. Some of the investigated reactions, such as the reduction of Cr(VI) by S2- or Fe2+ ions under anaerobic conditions, were instantaneous and the experimental results exactly followed the stoichiometric and equilibrium calculations. Other reactions, such as the reduction of Cr(VI) by organics in sediments and soils, or the oxidation of Cr(III) by MnO2, were much slower and clearly exhibited kinetic controls. Reduction of Cr(VI) by organics was dependent on both the type and amount of organic material. Dissolved oxygen by itself did not induce measurable oxidation of Cr(III), spiked to the experimental waters, after 128 days. Slow Cr(III) oxidation to Cr(VI) was only noted in one of the natural waters and sediments with half-lives ranging from 2 to 9 years. In all cases the extent of Cr(III) oxidation did not exceed 15% of the initial Cr(III) present. The overall results indicate that the transport and transformation of chromium can be predicted using kinetics data derived from a simplified laboratory experiment, the Eh-pH data and the aquatic system characteristics. Results of the microcosm and laboratory experiments were in good agreement with the predicted concentrations.     

The kinetics of hexavalent chromium reduction by metallic iron

The rate reduction of hexavalent chromium (Cr(VI)) by metallic iron under a range of conditions was studied in batch systems. The chemical variables studied were the Cr(VI) concentration, hydrogen ion concentration and surface area of iron. The influence of ionic strength and mixing rate was also examined. The reaction kinetics were found to be dependent on hydrogen ion concentration, hexavalent chromium concentration and iron surface area and to adhere to the following kinetic expression.

Full-size image (1K)

.The rate constant was evaluated and found to have a value of 5.45 × 10⁻⁵ 1 cm⁻² min⁻¹ over a wide range of conditions.The rate constant was found to increase as mixing rate increased up to a maximum value beyond which the rate was essentially independent of mixing. Increases in ionic strength were found to result in a rapid decrease in the rate constant at ionic strengths below 0.1 M. Further increases in ionic strength had no detectable impact on the rate constant. All rate determination studies were run in the mixing and ionic strength independent regions of these systems.Reaction stoichiometry was found to be, with one exception, independent of environmental conditions. In general, 1.33 mol of iron dissolved for each mol of Cr(VI) reduced. This highly efficient utilization of iron in the reduction suggests that hydrogen generated during iron dissolution may be acting as a reductant for the Cr(VI). The single parameter which influenced the reaction stoichiometry was the initial Cr(VI) concentration. The ratio of Cr(VI) reduced to iron dissolved increased rapidly as the Cr(VI) concentration increased. This observation was taken as being consistant with a surface interaction between the hexavalent chromium and some metastable hydrogen species at the iron surface.     

Removal of chromium (VI) from wastewater using bentonite-supported nanoscale zero-valent iron

Bentonite-supported nanoscale zero-valent iron (B-nZVI) was synthesized using liquid-phase reduction. The orthogonal method was used to evaluate the factors impacting Cr(VI) removal and this showed that the initial concentration of Cr(VI), pH, temperature, and B-nZVI loading were all importance factors. Characterization with scanning electron microscopy (SEM) validated the hypothesis that the presence of bentonite led to a decrease in aggregation of iron nanoparticles and a corresponding increase in the specific surface area (SSA) of the iron particles. B-nZVI with a 50% bentonite mass fraction had a SSA of 39.94 m²/g, while the SSA of nZVI and bentonite was 54.04 and 6.03 m²/g, respectively. X-ray diffraction (XRD) confirmed the existence of Fe⁰ before the reaction and the presence of Fe(II), Fe(III) and Cr(III) after the reaction. Batch experiments revealed that the removal of Cr (VI) using B-nZVI was consistent with pseudo first-order reaction kinetics. Finally, B-nZVI was used to remediate electroplating wastewater with removal efficiencies for Cr, Pb and Cu > 90%. Reuse of B-nZVI after washing with ethylenediaminetetraacetic acid (EDTA) solution was possible but the capacity of B-nZVI for Cr(VI) removal decreased by approximately 70%.     

Electrochemical treatment of effluents containing Cr(VI). Influence of pH and current on the kinetic

Compounds of Cr(VI) are very toxic and their reduction to Cr(III) is necessary to allow their further precipitation or adsorption. Chemical methods for Cr(VI) reduction are usually used for this purpose. As an alternative, electrochemical methods using three-dimensional electrodes, such as reticulated vitreous carbon (RVC) and polyaniline-modified RVC, have been used successfully. Since the pH affects reaction of Cr(VI) reduction, in this work its effect on the reaction rate was studied using electrodes of RVC and RVC/PANI. While a maximum in reaction rate was found for a pH 1.5 using the RVC, the RVC/PANI showed no differences in reaction rates in the range of pH between 0 and 1. Practically, no reaction was observed for any pH greater than 3. The effect of different current densities using optimized pH was also evaluated and the RVC/PANI electrode showed the best reaction rates, current efficiencies and energy consumption as a result of the polyaniline electrocatalytic effect.     

Bio-reduction of soluble chromate using a hydrogen-based membrane biofilm reactor

Hexavalent chromium (Cr(VI)) is a mutagen and carcinogen that is a significant concern in water and wastewater. A simple and non-hazardous means to remove Cr(VI) is bioreduction to Cr(III), which should precipitate as Cr(OH)3(s). Since Cr(VI)-reducing bacteria can use hydrogen (H2) as an electron donor, we tested the potential of the H2-based membrane biofilm reactor (MBfR) for chromate reduction and removal from water and wastewater. When Cr(VI) was added to a denitrifying MBfR, Cr(VI) reduction was immediate and increased over 11 days. Short-term experiments investigated the effects of Cr(VI) loading, H2 pressure, and nitrate loading on Cr(VI) reduction. Increasing the H2 pressure improved Cr(VI) reduction. Cr(VI) reduction also was sensitive to pH, with an optimum near 7.0, a sharp drop off below 7.0, and a gradual decline to 8.2. Cr(III) precipitated after a small upward adjustment of the pH. These experiments confirm that a denitrifying, H2-based MBfR can be used to reduce Cr(VI) to Cr(III) and remove Cr from water. The research shows that critical operational parameters include the H2 concentration, nitrate concentration, and pH.     

The acute lethal toxicity of heavy metals to peracarid crustaceans (with particular reference to fresh-water asellids and gammarids)

In static tests on the acute toxicity of metal salts to two fresh-water peracarids, Asellus aquaticus (L.) (Isopoda) and Crangonyx pseudogracilis Bousfield (Amphipoda), 48 and 96 h LC₅₀ values were determined for Al(III), Cd(II), Cr(III), Cu(II), Fe(III), Hg(II), Mn(II), Ni (II), Pb(II) and Zn(II). Additional metals tested upon Crangonyx alone were Ag(I), Co(II), Cr(VI), Fe(II), Mn(VII), Mo(VI), Sn(II) and V(V). Of the metal salts tested on both species, Asellus was more sensitive to Al(III) and Mn(II) than Crangonyx, similarly sensitive to Cd(II), Fe(III) and Zn(II), and less sensitive to the remainder. Toxicity of metal salts which are unstable with respect to reduction or oxidation was found to be higher than that of the corresponding stable salts of the same metal.Previously published data on the acute toxicity of heavy metal salts to fresh-water, estuarine and marine amphipods and isopods are tabulated and discussed. Brief comparisons are also made between the relative tolerances of peracarids, Daphnia and fresh-water fish. Crangonyx pseudogracilis is recommended as worthy of further research, due to its widespread distribution and ease of culture.     

Enhanced chitosan beads-supported Fe-nanoparticles for removal of heavy metals from electroplating wastewater in permeable reactive barriers

The removal of heavy metals from electroplating wastewater is a matter of paramount importance due to their high toxicity causing major environmental pollution problems. Nanoscale zero-valent iron (NZVI) became more effective to remove heavy metals from electroplating wastewater when enhanced chitosan (CS) beads were introduced as a support material in permeable reactive barriers (PRBs). The removal rate of Cr (VI) decreased with an increase of pH and initial Cr (VI) concentration. However, the removal rates of Cu (II), Cd (II) and Pb (II) increased with an increase of pH while decreased with an increase of their initial concentrations. The initial concentrations of heavy metals showed an effect on their removal sequence. Scanning electron microscope images showed that CS-NZVI beads enhanced by ethylene glycol diglycidyl ether (EGDE) had a loose and porous surface with a nucleus-shell structure. The pore size of the nucleus ranged from 19.2 to 138.6 μm with an average aperture size of around 58.6 μm. The shell showed a tube structure and electroplating wastewaters may reach NZVI through these tubes. X-ray photoelectron spectroscope (XPS) demonstrated that the reduction of Cr (VI) to Cr (III) was complete in less than 2 h. Cu (II) and Pb (II) were removed via predominant reduction and auxiliary adsorption. However, main adsorption and auxiliary reduction worked for the removal of Cd (II). The removal rate of total Cr, Cu (II), Cd (II) and Pb (II) from actual electroplating wastewater was 89.4%, 98.9%, 94.9% and 99.4%, respectively. The findings revealed that EGDE-CS-NZVI-beads PRBs had the capacity to remediate actual electroplating wastewater and may become an effective and promising technology for in situ remediation of heavy metals.     

Reduction of U(VI) by Fe(II) in the presence of hydrous ferric oxide and hematite: effects of solid transformation, surface coverage, and humic acid

Fe(II) was added to U(VI)-spiked suspensions of hydrous ferric oxide (HFO) or hematite to compare the redox behaviors of uranium in the presence of two different Fe(III) (oxyhydr)oxides. Experiments were conducted with low or high initial sorption density of U(VI) and in the presence or absence of humic acid (HA). About 80% of U(VI) was reduced within 3 days for low sorbed U(VI) conditions, with either hematite or HFO. The {Fe(3+)} in the low U(VI) experiments at 3 days, based on measured Fe(II) and U(VI) and the assumed presence of amorphous UO(2(s)), was consistent with control by HFO for either initial Fe(III) (oxyhydr)oxide. After about 1 day, partial re-oxidation to U(VI) was observed in the low sorbed U(VI) experiments in the absence of HA, without equivalent increase of dissolved U(VI). No reduction of U(VI) was observed in the high sorbed U(VI) experiments; it was hypothesized that the reduction required sorption proximity of U(VI) and Fe(II). Addition of 5mg/L HA slowed the reduction with HFO and had less effect with hematite. M?ssbauer spectroscopy (MBS) of (57)Fe(II)-enriched samples identified the formation of goethite, hematite, and non-stoichiometric magnetite from HFO, and the formation of HFO, hydrated hematite, and non-stoichiometric magnetite from hematite.     

The removal of chromium(VI) from dilute aqueous solution by activated carbon

The removal of chromium(VI) by activated carbon, filtrasorb 400, is brought by two major interfacial reactions: adsorption and reduction. Chemical factors such as pH and total Cr(VI) that affect the magnitude of Cr(VI) adsorption were investigated. The adsorption of Cr(VI) exhibits a peak value at pH 5–6. The particle size of carbon and the presence of cyanide species do not change the magnitude of chromium removal. The reduced Cr(VI), e.g. Cr(III) is less adsorbable than Cr(VI).The free energy of specific chemical interaction, ΔG^chem was computed by the Gouy-Chapman-Stern-Grahame model. The average values of ΔG^chem are −5.57 RT and −5.81RT, respectively, for Cr(VI) and CN. These values are significant enough to influence the overall magnitude of Cr(VI) and CN adsorption. Results also indicate that HCrO⁻₄ and Cr₂O²⁻₇ are the major Cr(VI) species involved in surface association.     

Removal of chromium from aqueous solutions and plating bath rinse by an electrochemical method

In this work, a bipolar packed bed electrolytic cell having steel Raschig rings behaving as electrodes has been used to remove chromium in the form of Cr(VI) from aqueous solutions and a sample of plating bath rinse.

Fe²⁺ ions generated at the anode side of the electrodes have reacted with OH^‐ ions generated at the cathode side forming Fe(OH)₂ in this electrolytic cell.Cr(VI) have coprecipitated as Cr(OH)₃ with Fe(OH)₃ forming after the redox reaction between Fe(OH)₂ and Cr(VI). Meanwhile other impurities have also removed besides Cr(VI) using this process. Removal rate of 100% for Cr(VI) has been achieved in the experiments done with different initial Cr(VI) concentration, duration of electrolysis and applied potential. Fully removal of Cr(VI) has also been achieved from the sample of plating bath rinse.     

Aqueous oxidation of dimethyl phthalate in a Fe(VI)-TiO(2)-UV reaction system

The application of a combined ferrate-photocatalysis process for the aqueous degradation of dimethyl phthalate (DMP) has been studied. The behaviour of the Fe(VI)-TiO(2)-UV process at pH 9 in the presence and absence of dissolved oxygen (DO) has been compared and significant differences have been found. In comparative tests under N(2) and O(2) bubbling, the chemical reduction rate of ferrate as conduction band electron acceptor was similar, but the resulting degradation of DMP was substantially lower in the presence of oxygen. It is speculated that the presence of oxygen leads to the formation of Fe-O-(organic) complex species that adsorb to, and deactivate, the surface of the photocatalyst. The presence of surface-adsorbed complex species was indicated by FTIR spectroscopy and a reduced TiO(2) adsorption capacity for DMP. In the presence of typical environmental levels of DO ( approximately 9mgL(-1)), the Fe(VI)-TiO(2)-UV process achieved a modest degree of DMP degradation (40% in 120min).     

Oxidation of suspected N-nitrosodimethylamine (NDMA) precursors by ferrate (VI): kinetics and effect on the NDMA formation potential of natural waters

The potential of ferrate (Fe(VI)) oxidation to remove N-nitrosodimethylamine (NDMA) precursors during water treatment was assessed. Apparent second-order rate constants (k(app)) for the reactions of NDMA and its suspected precursors (dimethylamine (DMA) and 7 tertiary amines with DMA functional group) with Fe(VI) were determined in the range of pH 6-12. Four model NDMA precursors (dimethyldithiocarbamate, dimethylaminobenzene, 3-(dimethylaminomethyl)indole and 4-dimethylaminoantipyrine) showed high reactivity toward Fe(VI) with k(app) values at pH 7 between 2.6 x 10(2) and 3.2 x 10(5)M(-1)s(-1). The other NDMA precursors (DMA, trimethylamine, dimethylethanolamine, dimethylformamide) and NDMA had k(app) values ranging from 0.55 to 9.1M(-1)s(-1) at pH 7. In the second part of the study, the NDMA formation potentials (NDMA-FP) of the model NDMA precursors and natural waters were measured with and without pre-oxidation by Fe(VI). For most of the NDMA precursors with the exception of DMA, a significant reduction of the NDMA-FP (>95%) was observed after complete transformation of the NDMA precursor. This result was supported by low yields of DMA from the Fe(VI) oxidation of tertiary amine NDMA precursors. Pre-oxidation of several natural waters (rivers Rhine, Neckar and Pfinz) with a high dose of Fe(VI) (0.38 mM = 21 mg L(-1) as Fe) led to removals of the NDMA-FP of 46-84%. This indicates that the NDMA precursors in these waters have a low reactivity toward Fe(VI) because it has been shown that for fast-reacting NDMA precursors Fe(VI) doses of 20 microM (1.1 mg L(-1) as Fe) are sufficient to completely oxidize the precursors.